WO2001027515A1 - Tuyau pour circulation d'eau chaude - Google Patents

Tuyau pour circulation d'eau chaude Download PDF

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Publication number
WO2001027515A1
WO2001027515A1 PCT/JP2000/006968 JP0006968W WO0127515A1 WO 2001027515 A1 WO2001027515 A1 WO 2001027515A1 JP 0006968 W JP0006968 W JP 0006968W WO 0127515 A1 WO0127515 A1 WO 0127515A1
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WIPO (PCT)
Prior art keywords
layer
pipe
multilayer
polymer particles
weight
Prior art date
Application number
PCT/JP2000/006968
Other languages
English (en)
Japanese (ja)
Inventor
Hiroyuki Shimo
Takashi Yamashita
Original Assignee
Kuraray Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kuraray Co., Ltd. filed Critical Kuraray Co., Ltd.
Priority to DE60041574T priority Critical patent/DE60041574D1/de
Priority to EP00964704A priority patent/EP1146273B1/fr
Priority to CA002353856A priority patent/CA2353856C/fr
Priority to US09/856,478 priority patent/US6447858B1/en
Publication of WO2001027515A1 publication Critical patent/WO2001027515A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L9/00—Rigid pipes
    • F16L9/12—Rigid pipes of plastics with or without reinforcement
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]

Definitions

  • the present invention relates to a multi-layer pipe, particularly a multi-layer pipe for hot water circulation used for central heating and centralized floor heating equipment by a hot water circulation method, wherein ethylene-butyl alcohol copolymer (A) 50 to 99% by weight And a multilayer pipe for warm water circulation having a layer of a thermoplastic resin composition (C) composed of 1 to 50% by weight of a polymer particle (B) having a multilayer structure.
  • Hot water circulation pipes have been mainly used for floor heating by the hot water circulation method.
  • Hot water circulation pipes are often buried in concrete during construction and installed under the floor, and once installed, it is very difficult to repair them afterwards. Is required.
  • plastic pipes that are less expensive than metal pipes and do not corrode the pipe material itself.
  • polyethylene, polypropylene, polybutene, or the like is used as such a plastic pipe material.
  • EVOH ethylene-vinyl alcohol copolymer
  • JP-A-6-140691 describes a hot water circulation pipe including an EVOH layer as an intermediate layer
  • JP-A-2-74341 discloses a hot-water circulation pipe having an EVOH layer as an outermost layer. The pipe is described. However, each of them has a problem that crack resistance is not always + minute.
  • EVOH has a problem derived from the rigidity of EVOH, although it has excellent oxygen barrier properties and mechanical strength (impact resistance) as described above.
  • EVOH is considered to be a very rigid resin compared to ordinary plastic resin.
  • Various studies have been made to improve the rigidity of this EVOH.
  • Japanese Patent Application Laid-Open No. Hei 10-24505 discloses that a multi-layered structure having a resin composition layer having excellent gas barrier properties and impact resistance comprising an EVOH resin and resin fine particles having a core-shell structure is used for a fuel container. Is described.
  • Japanese Patent Application Laid-Open No. 7-331020 describes a highly flexible resin composition comprising multilayer polymer particles having an epoxy group introduced therein and EVOH.
  • Japanese Patent Application Laid-Open No. H10-230555 describes that a multilayer pipe having a resin composition layer composed of an EVOH resin and an ethylene- (meth) acrylate resin and having excellent flexibility is used for a hot water circulation pipe. Have been.
  • cracks do not occur in the EVOH layer when the temperature at which the pipe is deformed is at room temperature (about 20 ° C).
  • areas where pipes for hot water circulation are used are generally in cold regions, so crack resistance is especially high when working in environments with very low outside temperatures (for example, at 15 ° C). Is not always sufficient, as clarified in the case example described below.
  • An object of the present invention is to solve the above problems. According to the present invention, there is provided a multilayer pipe for hot water circulation, which is excellent in oxygen barrier properties and crack resistance, especially crack resistance at low temperatures.
  • the present invention relates to a thermoplastic resin composition (C) layer comprising 50 to 99% by weight of an ethylene-butyl alcohol copolymer (A) and 1 to 50% by weight of a multilayered polymer particle (B).
  • the present invention relates to a multilayer pipe for hot water circulation having:
  • the multilayer structured polymer particles (B) have a hard layer as an outermost layer and a rubber layer inside.
  • the multilayer structure polymer particles (B) have reactivity or affinity for a hydroxyl group.
  • the multilayer polymer particles (B) have a carboxylic acid group in the hard layer.
  • the multilayer polymer particles (B) have an epoxy group in the hard layer.
  • thermoplastic resin composition (C) layer is the outermost layer of the hot water circulation pipe.
  • the heat obtained by blending the multilayer polymer particles (B) with the EVOH (A) is improved.
  • the greatest feature is to use the layer of the plastic resin composition (C).
  • the multilayer polymer particles (B) preferably have a hard layer as the outermost layer and have a rubber layer inside, and a blend of EVOH (A) and multilayer polymer particles (B).
  • the EVOH (A) used in the present invention those obtained by saponifying an ethylene monobutyl ester copolymer are preferable.
  • the ethylene content is 15-70 mol 0 /. , More preferably 20 to 65 mole 0/0, and optimally 25 to 60 mol. / 0 .
  • Ethylene content poor melt moldability is less than 1 5 mole 0/0, there is a possibility that water resistance and hot water resistance decreases.
  • gas barrier properties may be insufficient.
  • the saponification degree of the butyl ester component is preferably 85% or more, more preferably 90% or more. If the degree of saponification is less than 85%, gas barrier properties and thermal stability may deteriorate. Further, if the ethylene content exceeds 70 mol% or the saponification degree is less than 85%, the gas barrier properties may be reduced.
  • a typical example of the vinyl ester used in the production of EVOH (A) is vinyl acetate, but other fatty acid vinyl esters (such as vinyl propionate and vivalate) can also be used.
  • EVOH (A) is a copolymer component in an amount of 0.0002 to 0.2 mol of a silane compound. / 0 can be contained.
  • the vinylsilane compound for example, examples thereof include burtrimethoxysilane, burtriethoxysilane, vinyltri (] 3-methoxy-ethoxy) silane, and ⁇ -methacryloxypropylmethoxysilane. Of these, butyltrimethoxysilane and vinyltriethoxysilane are preferably used.
  • monomers such as propylene, butylene, or unsaturated carboxylic acids such as (meth) acrylic acid, methyl (meth) acrylate, and ethyl (meth) acrylate may be used as long as the object of the present invention is not hindered.
  • An acid or an ester thereof or butylpyrrolidone such as bi-pyrrolidone may be copolymerized.
  • the preferred melt flow rate (MFR) of the E VOH ( ⁇ ) used in the present invention (at 190 ° C. under a load of 2160 g) is 0.:! To 50 gZl 0 min., Optimally 0. 5 to 30 gZl Omin. However, although the melting point is around 190 ° C or higher than 190 ° C, the MFR is measured under a load of 2160 g at a plurality of temperatures above the melting point. Plotted on the vertical axis, extrapolated to 190 ° C.
  • EVOH (A) may be a single EVOH or a mixture of two or more EVOHs.
  • the multilayer polymer particles (B) used in the present invention are particles having at least a hard layer and a rubber layer. Either layer may be the outermost layer, but it is preferable to have a hard layer as the outermost layer and a rubber layer inside.
  • the rubber layer here refers to a polymer layer having a glass transition temperature (hereinafter sometimes referred to as Tg) of 25 ° C or lower, and the hard layer refers to a polymer layer having a Tg higher than 25 ° C.
  • Tg glass transition temperature
  • the multilayer polymer particles (B) may be composed of two layers, may be composed of three layers, or may be composed of four or more layers.
  • a rubber layer (center layer) and a Z hard layer (outermost layer) are used.
  • a hard layer (center layer) Z rubber layer (intermediate layer) Z hard layer ( Rubber layer (center layer) Rubber layer (middle layer) Hard layer (outermost layer) or rubber layer (center layer) It has a configuration of Z hard layer (intermediate layer) / hard layer (outermost layer).
  • the composition of the rubber layer of the multilayer polymer particles (B) used in the present invention are no particular restrictions on the composition of the rubber layer of the multilayer polymer particles (B) used in the present invention.
  • preferred polymers for the constitution include polybutadiene, polyisoprene, and butadiene-isoprene copolymer.
  • Conjugated polymers such as copolymers, polychloroprene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, acrylate-butadiene copolymer, hydrogenated products of this conjugated gen-based polymer, ethylene-propylene Olefin rubbers such as copolymers, acryl rubbers such as polyacrylates, polyorganosiloxanes, thermoplastic elastomers, and ethylene ionomer copolymers.One or more of these can be used. Is done. Among them, an acrylic rubber, a conjugated polymer or a hydrogenated product of a conjugated polymer is preferable.
  • Acrylic rubber is formed by polymerizing an acrylate ester.
  • the acrylates include alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and octyl acrylate. Among them, butyl acrylate or ethyl acrylate is preferred.
  • the acrylic rubber or conjugated gen-based polymer is mainly produced by polymerizing a monomer system composed of alkyl acrylate and / or a conjugated gen-based compound.
  • This acrylic rubber or conjugated gen-based polymer can be obtained by copolymerizing another monofunctional polymerizable monomer in addition to the above monomer, if necessary.
  • Other monofunctional polymerizable monomers that can be copolymerized include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and methacrylic acid.
  • methacrylates such as benzyl, naphthyl methacrylate, and isobutyl methacrylate
  • aromatic vinyl compounds such as styrene and ⁇ -methylstyrene
  • the other single-functional polymerizable monomer is desirably 20% by weight or less of the entire polymerizable monomer forming the rubber layer.
  • the rubber layer forming a part of the multilayer polymer particles ( ⁇ ) used in the present invention preferably has a cross-linked molecular chain structure in order to exhibit rubber elasticity. It is preferable that the molecular chain of the compound and the molecular chain in the layer adjacent thereto are grafted by a chemical bond. For that purpose, in the monomer polymerization for forming the rubber layer, it may be preferable to use a small amount of a polyfunctional polymerizable monomer in combination as a crosslinking agent or a grafting agent.
  • a polyfunctional polymerizable monomer is a monomer having two or more carbon-carbon double bonds in the molecule, for example, unsaturated forces such as acrylic acid, methacrylic acid, and cinnamic acid.
  • unsaturated forces such as acrylic acid, methacrylic acid, and cinnamic acid.
  • Esteranol with unsaturated alcohols such as allylic alcohol and methallyl alcohol or glycols such as ethylene glycolone and butanediol; and dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and maleic acid with the above unsaturated acids Esters with alcohols and the like are included.
  • polyfunctional polymerizable monomers include acrylyl acrylate, methallyl acrylate, methacrylic acid, methallyl methacrylate, acrylyl cinnamate, methallyl cinnamate, diaryl maleate, diaryl phthalate, and terephthalic acid.
  • examples thereof include diaryl, diaryl isophthalate, dibibenzene, ethylene glycol di (meth) acrylate, butandiol di (meth) acrylate, and hexanediol di (meth) acrylate.
  • the above-mentioned term “di (meta) atari rate” It means the general term for "diatalylate” and "dimetatalylate”. These may be used alone or in combination of two or more. Among them, aryl methacrylate is preferably used.
  • the amount of the polyfunctional polymerizable monomer used is preferably limited to 10% by weight or less of the entire polymerizable monomer forming the rubber layer. This is because if the amount of the polyfunctional polymerizable monomer is too large, it is considered that the performance as a rubber is reduced, and the flexibility of the thermoplastic resin composition is reduced.
  • a monomer system containing a conjugated diene compound as a main component it does not necessarily need to be used in combination with a polyfunctional polymerizable monomer because it itself functions as a crosslink or a graph point. .
  • radical polymerizable monomer examples include: alkyl methacrylate such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate; Methacrylic esters having an alicyclic skeleton such as hexyl, isobornyl methacrylate, and adamantyl methacrylate; methacrylic esters having an aromatic ring such as phenyl methacrylate; aromatic vinyl compounds such as styrene and ⁇ -methylstyrene; and acrylonitrile Is exemplified.
  • alkyl methacrylate such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate
  • Methacrylic esters having an alicyclic skeleton such as hexyl, isobornyl methacrylate, and adamantyl methacrylate
  • radically polymerizable monomers can be used alone or in combination of two or more.
  • Preferred examples of the radical polymerizable monomer system include methyl methacrylate or styrene alone or a combination of two or more radical polymerizable monomers containing the same as a main component.
  • the dispersion of the multilayer polymer particles ( ⁇ ) in EVOH ( ⁇ ) Thermoplastic resin composition with improved properties The gas barrier property and / or crack resistance of the layer (c) is improved, and the crack resistance of the hot water circulation pipe obtained by using this composition is improved.
  • a functional group having reactivity or affinity for a hydroxyl group or a form in which the functional group is protected or protected is preferable to use a radical polymerizable compound having a functional group.
  • the copolymerizable compound which is preferably used for forming the above functional group of the multilayer polymer particles (B) and has a reactivity or an affinity for a hydroxyl group includes EVOH under the following mixing conditions.
  • Unsaturated compounds having a group capable of forming a chemical bond by reacting with a hydroxyl group in (A) or a group capable of forming an intermolecular bond such as a hydrogen bond with a hydroxyl group are exemplified.
  • the functional group having reactivity or affinity for the hydroxyl group include, for example, an acid group such as a hydroxyl group, an epoxy group, an isocyanate group (_NCO), a carboxyl group, and a maleic anhydride.
  • An acid anhydride group, a group whose protective group comes off under the following mixing conditions, and changes to any of the above groups, and the like can be given.
  • copolymerizable compounds having reactivity or affinity for a hydroxyl group include (meth) acrylic acid 2-hydroxyl, (meth) acrylic acid 3_hydroxypropyl, and crotonic acid 2-hydroxyl.
  • Glycidyl acrylate a polymerizable compound having a hydroxyl group, such as 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-1-butene, trans-4-hydroxy-2-butene
  • (meth) atarylate is a generic term for “atarylate” and “metharylate”
  • (meth) acrylic acid is “acrylic acid” and “methacrylic acid”. Means a generic term.
  • an acid group such as a hydroxyl group, an acid anhydride group derived from maleic anhydride, and an epoxy group are preferable.
  • an acid group such as a carboxyl group or an epoxy group is particularly preferred.
  • the copolymerizable compound having an acid group such as a carboxyl group include methacrylic acid and acrylic acid
  • examples of the copolymerizable compound having an epoxy group include glycidyl methacrylate and glycidyl acrylate. .
  • the amount of the copolymerizable compound having a functional group having reactivity or affinity for a hydroxyl group or a functional group in a protected form thereof is determined according to the amount of the multi-layer polymer particles (B).
  • the content is preferably from 0.01 to 75% by weight, more preferably from 0.1 to 40% by weight, based on the whole monomer.
  • the above-mentioned protecting group is a group which is deviated under the conditions of miscibility with EVOH (A) as described later and gives the functional group, and may be any group which does not inhibit the object of the present invention.
  • Examples of the copolymerizable compound having a protected functional group include t_butyl methacrylcarbamate and the like.
  • the multilayer polymer particles (B) have a functional group having reactivity or affinity for a hydroxyl group
  • this functional group is preferably present on the molecular chain in the outermost hard layer.
  • this functional group is capable of substantially reacting with a hydroxyl group in EVOH (A) or forming an intermolecular bond, It may be present in each of the layers (the outermost layer, the intermediate layer, and the inner layer) of the multilayer polymer particles (B).
  • the content of the rubber layer in the multilayer polymer particles (B) is in the range of 50 to 90% by weight. Preferably, it is within the range.
  • the spherical multilayer polymer particles (B) can be obtained by following the usual emulsion polymerization method. Can be easily obtained. Emulsion polymerization is carried out according to a method commonly used by those skilled in the art, and if necessary, a chain transfer agent such as octyl mercaptan or lauryl mercaptan can be used. After the emulsion polymerization, the multilayer polymer particles (B) are separated from the polymer latex and obtained according to a method commonly used by those skilled in the art (for example, a method such as coagulation and drying).
  • a method such as coagulation and drying
  • the average particle diameter of each of the obtained multilayer polymer particles (B) is preferably in the range of 0.02 to 2 ⁇ m, more preferably in the range of 0.05 to 1.0 / m. preferable.
  • the form of the multilayer polymer particles (B) to be produced is not particularly limited. For example, a state in which the multilayer polymer particles (B) are fused or agglomerated at the outermost layer.
  • thermoplastic resin composition (C) It may be in the form of pellets, powders, or granules (hereinafter, sometimes referred to as aggregated particles). Even in a completely independent form and in a form of a misalignment of the aggregated particles, it can be used for producing the thermoplastic resin composition (C).
  • the obtained multilayer polymer particles (B) are dispersed in EVOH (A) to produce the thermoplastic resin composition (C) used in the present invention.
  • the weight ratio (AZB) between EVOH (A) and multilayer polymer particles (B) is It is preferable to be in the range of 99Zl to 50/50% by weight from the balance of the rear property.
  • thermoplastic resin composition (C) used in the present invention is produced by a method appropriately used by those skilled in the art. For example, when the melt mixing method is used, EVOH ( ⁇ ) and multilayer polymer particles ( ⁇ ) and, if desired, stabilizers, dyes, pigments, plasticizers, lubricants, fillers, antioxidants and other resins, etc. May be added and mixed, and then melt-kneaded at a temperature of, for example, 200 to 300 ° C. using a screw type extruder or the like.
  • the dispersion state of the multilayer polymer particles (B) in the EVOH (A) is not particularly limited.
  • the state may be a state in which the particles are uniformly dispersed in the form, or a state in which completely independent particles and aggregated particles are uniformly dispersed while being mixed.
  • the dispersed multi-layered polymer particles (B) preferably have an average particle diameter of 10 ⁇ or less, including a completely independent form and a form of aggregated particles, and are 5 / in or less.
  • the particles having an average particle diameter in the range of 0.03 to 1 ⁇ m are uniformly dispersed in EVOH (A). If the particle size of the dispersed particles exceeds ⁇ ⁇ , it becomes difficult for the multilayer polymer particles ( ⁇ ⁇ ⁇ ) to be uniformly dispersed in the matrix of the EVOH (A), and as a result, crack resistance is reduced.
  • Stabilizers that can be blended with the thermoplastic resin composition (C) used in the present invention include oxidation stabilizers, heat stabilizers, and ultraviolet stabilizers. Those which can be used and are generally used for addition polymers are preferred.
  • oxidation stabilizer or heat stabilizer examples include one or more of sterically hindered phenols, hydroquinones, and phosphates.
  • ultraviolet stabilizer examples include various substituted resorcinols, salicylates, benzotriazole, and benzophenone.
  • thermoplastic resin composition (C) used in the present invention contains an antioxidant in addition to the above resin.
  • Antioxidants include, for example, 3,5-t-butyl 4-hydroxylluene, ilganox 101 (product name: Ciba-Geigy), ilganox 11076 (product name: Ciba-Geigy) and the like.
  • other suitable additives eg, heat stabilizers, plasticizers, UV absorbers, colorants, fillers, other resins, etc.
  • suitable additives eg, heat stabilizers, plasticizers, UV absorbers, colorants, fillers, other resins, etc.
  • thermoplastic resin composition (C) layer comprising 50 to 99% by weight of the EVOH (A) and 1 to 50% by weight of the multilayer polymer particles (B) is: Force that can be formed into a single-layered molded product composed of only the thermoplastic resin composition (C) layer. Multi-layered molding of the thermoplastic resin composition (C) layer and another thermoplastic resin (E) layer. It is more preferable to make a product.
  • the resin forming the thermoplastic resin (E) layer adjacent to the thermoplastic resin composition (C) layer may be high-density, medium-density, or low-density polyethylene, vinyl acetate, acrylate, or butene.
  • thermoplastic resin (E) layer Polyamide resin, polyester resin, polystyrene resin, polyvinyl chloride resin, acrylic resin, polyurethane resin, polycarbonate resin, and polyvinyl acetate resin. Resins.
  • an adhesive resin (F) layer is provided between the thermoplastic resin composition (C) layer constituting the multilayer of the hot water circulation pipe of the present invention and the adjacent thermoplastic resin (E) layer. Is also good.
  • the adhesive resin (F) is not particularly limited. Unsaturated carboxylic acids or their anhydrides (such as maleic anhydride) can be converted to olefin-based polymers or copolymers (eg, LLDPE, VLDPE, etc.), ethylene monoacetate vinyl copolymers, ethylene mono (meth) acrylic acid A typical example is a product grafted to an ester copolymer.
  • the method for producing the pipe for hot water circulation of the present invention is not particularly limited. For example, a co-extrusion molding operation using two or three extruders and a circular die for multilayering can obtain an endless pipe most efficiently.
  • the layer structure of the multilayer structure (pipe) is not particularly limited. Considering moldability and cost, (outer) thermoplastic resin (E) layer Z thermoplastic resin composition (C) layer / thermoplastic resin (E) layer (inner), (outer) thermoplastic resin composition Material (C) layer / Adhesive resin (F) layer Thermoplastic resin (E) layer (Inner), (Outer) thermoplastic resin (E) layer Z adhesive resin (F) layer Z thermoplastic resin composition ( C) Layer Z Adhesive resin (F) Layer Thermoplastic resin (E) Layer (inner) etc. are typical examples. When a thermoplastic resin (E) layer is provided on both outer layers, different resins may be used, or the same resin may be used.
  • thermoplastic resin composition (C) layer is the outermost layer of the pipe.
  • thermoplastic resin composition (C) layer is the outermost layer of the pipe.
  • conventional resins are inferior in crack resistance, so even if a gas barrier resin is used for the outer layer, if cracks occur, the commercial value of the pipes for hot water circulation will be remarkable due to the deterioration of appearance and the decrease in barrier properties Be impaired.
  • thermoplastic resin composition (C) used in the present invention has excellent gas-barrier properties and crack resistance.
  • the multi-layer pipe for hot water circulation of the present invention produced by the above method or the like is useful as a pipe for hot water circulation having excellent gas barrier properties and crack resistance, especially crack resistance at low temperatures.
  • the multilayer pipe for hot water circulation of the present invention can be used as a pipe for various liquids or gas. That is, the term “for hot water circulation” of the present invention also includes applications for circulation of various liquids and gases.
  • Table 1 shows the EVOH resin used in Examples and Comparative Examples of the present invention.
  • the particle size of the multilayer polymer particles (B-3) in the latex thus obtained was measured by a dynamic light scattering method using a laser particle size analysis system PAR-II (Otsuka Electronics Co., Ltd.). As a result, the average particle size of the multilayer polymer particles (B-3) was 0.20 / Xm.
  • Synthesis Example 4 Production of multilayer polymer particles 1 Under a nitrogen atmosphere, 600 parts by weight of distilled water, 0.15 parts by weight of sodium lauryl sarcosinate as an emulsifier and 1.3 parts by weight of sodium stearate were placed in a polymerization vessel equipped with a stirring blade, a cooling pipe and a dropping funnel. In addition, the mixture was heated to 70 ° C and uniformly dissolved.
  • Ethylene content 32 mol%, saponification degree 99.5 mole 0/0, MFR (1 90.C , 21 60 under g load) 1. 6 g / 10 min, melting point 1 83 ° C EVOH (A- 1 )
  • a dry blend consisting of 90 parts by weight and 10 parts by weight of the multilayer polymer particles (B-1) obtained in Synthesis Example 1 was placed in a twin-screw type vented extruder, and dried under nitrogen. The pellet was extruded at ° C to obtain a pellet of an EVOH-based resin composition (C-11).
  • HDPE high-density polyethylene
  • E- 1 thermoplastic resin
  • the oxygen barrier property was evaluated by the rate of increase of dissolved oxygen. The smaller the rate of increase of dissolved oxygen, the better the oxygen barrier properties.
  • the water from which dissolved oxygen was removed was circulated through the obtained pipe using a packed tower filled with metallic tin, and at a temperature of 70 ° C, the rate of increase of dissolved oxygen in the water was increased to 20 ° C and 65% R. It was measured under the condition of H. As a result, the rate of increase of the dissolved oxygen was 25 mu [delta] Zeta liters ⁇ hr.
  • the increasing rate of g liter ⁇ hr indicates that there is an increase in dissolved oxygen at a rate of / zg / hr per liter of water in the pipe.
  • the volume of water in the entire system including the pipe is V 1 cc
  • the volume of water in the pipe is V 2 cc
  • the oxygen concentration increase in the circulating water in the unit per unit time is Bzg / liter *.
  • the pipe having the above-described configuration was manufactured continuously for 1 hour, and the amount of the die attached was visually observed.
  • Example 5 Example 5
  • a multi-layer pipe was prepared in the same manner as in Example 1 except that a dry blend was used, which was composed of 80 parts by weight of EVOH (A-1) and 20 parts by weight of the multilayer polymer particles (B-1). , evaluated. Table 2 shows the results.
  • Example 6
  • a multilayer pipe was prepared and evaluated in the same manner as in Example 1 except that EVOH (A-2) was used instead of EVOH (A-1). Table 2 shows the results. Comparative Example 1
  • a multilayer pipe was prepared and evaluated in the same manner as in Example 1, except that only the EVOH (A-1) resin was used instead of the EVOH-based resin composition (C-1). Table 2 shows the results. Comparative Example 2
  • a multi-layer pipe was prepared in the same manner as in Example 1 except that a dry blend was made of 40 parts by weight of EVOH (A-1) and 60 parts by weight of multi-layer polymer particles (B_l). evaluated. Table 2 shows the results. Comparative Examples 3 and 4 Instead of the multilayer polymer particles, an ethylene-methacrylic acid copolymer (Niutarel 0309HC manufactured by Mitsui DuPont, methacrylic acid content: 9% by weight, Comparative Example 3), maleic anhydride-modified linear low-density polyethylene (Mitsui A multi-layer pipe was prepared and evaluated in the same manner as in Example 1 except that the chemical product NF 468A and Comparative Example 4) were used. Table 2 shows the results. Table 2
  • EMAA Ethylene-methacrylic acid copolymer (Nucrel 0309HC manufactured by Mitsui 'i-hon')
  • mLLDPE Maleic anhydride-modified linear low-density polyethylene I-styrene (Mitsui Chemicals ad; -NF468A)
  • Comparative Example 1 Nearly 80 to 90% of the multilayer pipes of Comparative Example 1 having an EVOH layer containing no multilayer polymer particles (B) generated large cracks.
  • Comparative Example 2 having an EVOH layer in which the content of the multilayer polymer particles (B) exceeds 50% by weight
  • the layered pipe showed good results in terms of crack resistance, but was inferior in oxygen barrier properties.
  • the multi-layer pipe of Comparative Example 3 having an EVOH layer using an ethylene-methacrylic acid copolymer instead of the multi-layer polymer particles (B) showed good results in terms of oxygen barrier properties. Satisfactory results were not obtained for extrusion die adhesion, especially crack resistance.
  • the multilayer pipe of Comparative Example 4 having an EVOH layer using a maleic anhydride-modified linear low-density polyethylene instead of the multilayer-structured polymer particles (B) exhibited oxygen barrier properties and crack resistance. Showed good results, but no satisfactory results were obtained for extrusion die adhesion.
  • the multilayer pipe of the present invention having the EVOH composition (C) layer containing 10 to 20% by weight of the multilayer structure polymer particles (B) hardly generates cracks and has gas barrier properties. It has excellent crack resistance and was shown to be suitable as a hot water circulation pipe.
  • a hot water circulation pipe having a resin composition having excellent performance in gas barrier properties and crack resistance, especially crack resistance at low temperatures.

Abstract

Ce tuyau multicouche pour circulation d'eau chaude comprend une composition de résine thermoplastique comprenant (A) pour 50% à 99% de sa masse un copolymère d'éthylène/alcool vinylique, et (B) pour 1% à 50% de sa masse des particules de polymère en plusieurs couches. Ce tube présente d'excellentes propriétés de barrière contre l'oxygène et une bonne résistance aux craquelures, particulièrement aux basses températures.
PCT/JP2000/006968 1999-10-08 2000-10-05 Tuyau pour circulation d'eau chaude WO2001027515A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
DE60041574T DE60041574D1 (de) 1999-10-08 2000-10-05 Rohr für heisswasserzirkulation
EP00964704A EP1146273B1 (fr) 1999-10-08 2000-10-05 Tuyau pour circulation d'eau chaude
CA002353856A CA2353856C (fr) 1999-10-08 2000-10-05 Tuyau pour circulation d'eau chaude
US09/856,478 US6447858B1 (en) 1999-10-08 2000-10-05 Pipe for hot-water circulation

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP11/288782 1999-10-08
JP28878299 1999-10-08

Publications (1)

Publication Number Publication Date
WO2001027515A1 true WO2001027515A1 (fr) 2001-04-19

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PCT/JP2000/006968 WO2001027515A1 (fr) 1999-10-08 2000-10-05 Tuyau pour circulation d'eau chaude

Country Status (9)

Country Link
US (1) US6447858B1 (fr)
EP (1) EP1146273B1 (fr)
KR (1) KR100475784B1 (fr)
CN (1) CN1172101C (fr)
AT (1) ATE423290T1 (fr)
CA (1) CA2353856C (fr)
DE (1) DE60041574D1 (fr)
ES (1) ES2317850T3 (fr)
WO (1) WO2001027515A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011125736A1 (fr) * 2010-03-31 2011-10-13 株式会社クラレ Composition de résine, article moulé, tuyau multicouche et procédé pour produire celui-ci
WO2020179811A1 (fr) * 2019-03-04 2020-09-10 株式会社クラレ Composition de résine et structure multicouche l'utilisant

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2313399C (fr) * 1999-07-08 2005-02-15 Kuraray Co., Ltd. Compositions de resine thermoplastique et contenant multicouche comprenant ces compositions
JP2004169851A (ja) * 2002-11-21 2004-06-17 Sanoh Industrial Co Ltd 多層チューブ
US20090286028A1 (en) * 2008-05-01 2009-11-19 Wayne Edward Garver Multi-layered fuel tubing
JP5360803B2 (ja) * 2008-10-14 2013-12-04 株式会社トヨックス ガスバリア性合成樹脂管
GR20080100806A (el) * 2008-12-18 2010-02-24 Νικολαος Κυραδης Πολυστρωματικος πλαστικος σωληνας βελτιωμενης διαστρωματικης συνδεσης, βελτιωμενων μηχανικων ιδιοτητων και χαμηλης γραμμικης διαστολης με αντιδραστικη συνεξωθηση
US8997880B2 (en) 2012-01-31 2015-04-07 Wagon Trail Ventures, Inc. Lined downhole oilfield tubulars
DE102012106061A1 (de) * 2012-07-06 2014-01-09 Rehau Ag + Co Verwendung einer Polymerzusammensetzung
KR102259572B1 (ko) 2013-06-18 2021-06-02 사우디 베이식 인더스트리즈 코포레이션 파이프용 산소 차단 필름
US20220081546A1 (en) * 2018-12-21 2022-03-17 Kuraray Co., Ltd. Composition, coating, film, and base material

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61140691A (ja) 1984-12-12 1986-06-27 株式会社クラレ パイプ
JPH0274341A (ja) 1988-09-09 1990-03-14 Nippon Synthetic Chem Ind Co Ltd:The 温水循環用パイプ
JPH07331020A (ja) 1994-06-02 1995-12-19 Kureha Chem Ind Co Ltd 熱可塑性樹脂組成物
JPH1024505A (ja) 1996-07-09 1998-01-27 Kuraray Co Ltd 燃料容器および燃料パイプ
JPH10230555A (ja) 1997-02-19 1998-09-02 Kuraray Co Ltd 多層パイプおよびその用途

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0814126B1 (fr) * 1996-06-18 2000-09-13 Kuraray Co., Ltd. Compositions polymères d'éthylène-alcool vinylique et leur utilisation
US5972447A (en) 1996-09-30 1999-10-26 Kuraray Co., Ltd. Thermoformable multilayer film and thermoformed container

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61140691A (ja) 1984-12-12 1986-06-27 株式会社クラレ パイプ
JPH0274341A (ja) 1988-09-09 1990-03-14 Nippon Synthetic Chem Ind Co Ltd:The 温水循環用パイプ
JPH07331020A (ja) 1994-06-02 1995-12-19 Kureha Chem Ind Co Ltd 熱可塑性樹脂組成物
JPH1024505A (ja) 1996-07-09 1998-01-27 Kuraray Co Ltd 燃料容器および燃料パイプ
JPH10230555A (ja) 1997-02-19 1998-09-02 Kuraray Co Ltd 多層パイプおよびその用途

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011125736A1 (fr) * 2010-03-31 2011-10-13 株式会社クラレ Composition de résine, article moulé, tuyau multicouche et procédé pour produire celui-ci
JPWO2011125736A1 (ja) * 2010-03-31 2013-07-08 株式会社クラレ 樹脂組成物、成形体、多層パイプ及びそれらの製造方法
JP5828187B2 (ja) * 2010-03-31 2015-12-02 株式会社クラレ 温水循環用多層パイプ及びその製造方法
US9290636B2 (en) 2010-03-31 2016-03-22 Kuraray Co., Ltd. Resin composition, molded article, multilayered pipe and method for producing the same
US9605130B2 (en) 2010-03-31 2017-03-28 Kuraray Co., Ltd. Resin composition, molded article, multilayered pipe and method for producing the same
WO2020179811A1 (fr) * 2019-03-04 2020-09-10 株式会社クラレ Composition de résine et structure multicouche l'utilisant

Also Published As

Publication number Publication date
CN1327526A (zh) 2001-12-19
EP1146273B1 (fr) 2009-02-18
EP1146273A4 (fr) 2005-06-15
KR20010080698A (ko) 2001-08-22
CA2353856C (fr) 2007-10-30
KR100475784B1 (ko) 2005-03-10
ATE423290T1 (de) 2009-03-15
CN1172101C (zh) 2004-10-20
CA2353856A1 (fr) 2001-04-19
DE60041574D1 (de) 2009-04-02
ES2317850T3 (es) 2009-05-01
EP1146273A1 (fr) 2001-10-17
US6447858B1 (en) 2002-09-10

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